JPS61231092A - Pulverized coal-oil mixed fuel composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition which can maintain an excelelnt dispersion stability for a long period of time, CONSTITUTION:40-60pts.wt. coal powder such as Miike coal powder is mixed with 60-40 pts.wt. petroleum.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a pulverized coal-oil mixed fuel composition used as a liquid fuel, which is made by suspending and stabilizing fine coal powder in petroleum-based heavy oil. It is about improvement.

Currently, most of the world's energy is provided by oil, but there are limits to the reserves of oil resources.
In the near future, there is a possibility that we will not be able to meet the increasing energy demand. Coal has recently been attracting attention as an energy source to replace oil. Coal is considered to be an extremely promising resource due to its abundant reserves and the wide range of production areas.

When coal is mined, it is lumpy and difficult to handle, so it is being considered to turn it into pulverized coal, suspend it in heavy petroleum oil, and use it as a liquid fuel.

Conventional technology If coal is simply suspended in heavy oil, the suspension is unstable and pulverized coal tends to settle out over time. It is known that pulverized coal can be stabilized by reducing its particle size and ultrafinely pulverizing it to 0.1 to 10 microns, but ultrafinely pulverizing it is not easy (and is economically disadvantageous).

Therefore, pulverized coal pulverized to about 200 mesh is suspended in heavy oil, and additives such as surfactants are added thereto to stabilize the suspension. Additives conventionally used for this purpose include various fatty acids and soaps, a combination of lead oleate and alkali, soft or hard sodium dodecylbenzenesulfonate, EDTA derivatives, dialkyl sulfosuccinic acid, and octadecyl. Betaine, polyethylene polyamine-based copolymerized preconditioned high molecular weight nonionic surfactant, sorbitol
Propylene oxide-ethylene oxide copolymer type nonionic surfactants are used.

Problems to be Solved by the Invention However, additives that can be used in pulverized coal oil mixed fuel compositions are expensive and economically disadvantageous.

The present invention was made in view of the above circumstances, and provides an additive that is inexpensive, effectively prevents separation of the composition, maintains low viscosity, and obtains a composition with good dispersion stability. The purpose is to

As a means to defuse the problem, the present invention provides a mixture of 40 to 60 parts by weight of coal powder and 40 to 60 parts by weight of petroleum heavy oil to 95 to 99.5% by weight, and the addition of toll as an additive. oil or tall oil fat 11
It is characterized by adding 0.5 to 5% by weight.

In general, coal has a different composition depending on its production area.
There are differences in their characteristics. Miike charcoal, which has a low water content, is most suitable for use in the composition of the present invention, and the effect of stabilizing dispersion according to the present invention is most significant, but coal from other regions can also be used. It is possible and sufficiently effective.

The moisture content in the coal is preferably as low as possible. If the water content is high, the coal tends to settle over time, which is not preferable. Therefore, even when using the Miike charcoal, it is preferable to dry it before preparing the composition. However, when the moisture content is high, even if the coal settles over time, the settled coal will not solidify at the bottom of the composition liquid, and will be easily homogenized by gentle stirring, so that it can be used as a liquid fuel. Since there is no problem in using it,
Moisture content in the coal is not an essential requirement of the present invention.

As the heavy oil, normal C heavy oil can be used,
There is no problem with the place of production.

The ratio of coal powder to heavy oil can be in the range of 40 to 60% coal powder to 40 to 60% heavy oil, and both are usually mixed in equal amounts. When the amount of coal powder is less than 40%, the amount of coal is small, and the meaning of reducing oil consumption by using a mixed fuel is lost. 60 again
% or more, a sufficiently stable composition can be obtained according to the present invention, but the viscosity of the composition becomes too high, making it difficult to handle.

The amount of tall oil or tall oil fatty acid added to the composition of the present invention is suitably 0.5 to 5% by weight based on the total composition. In addition, hereinafter, when referring to tall oil in this specification, tall oil fatty acids are also included.

The appropriate amount of tall oil to be added differs depending on the region of coal production; with Miike charcoal, a sufficiently stable composition can be obtained at 0.5 to 1% by weight, but coal from other regions can be used. In some cases, it is necessary to increase the amount by 2 to 5% by weight depending on the production area. The appropriate amount of addition also varies depending on the particle size of the coal powder, and if the particle size is large, it is necessary to increase the amount of tall oil added. However, once the necessary amount of tall oil is added depending on the origin and particle size of the coal powder, the effect will not increase even if the amount of tall oil added is increased further.

To prepare the composition of the present invention, heavy oil is heated to about 70°C, and predetermined amounts of tall oil and coal powder are added thereto.
Prepare by stirring with a stirrer for about 3 minutes.

When preparing the composition II, water can be added in small amounts. A predetermined amount of tall oil and 0.1 to 3% by weight of water based on the entire composition are added to heavy oil to homogenize it, and a predetermined amount of coal powder is added to this and stirred to prepare a composition. do. Although the composition obtained in this way has a slightly higher viscosity than one without the addition of water, it has less settling of coal powder and is less likely to change over time, making it an extremely excellent fuel composition. Become a thing. This fact contradicts the fact that a high water content in coal powder is undesirable as mentioned above, and the behavior of water in the composition is not clear.

Function: In the composition of the present invention, higher fatty acids and resin acids in tall oil adsorb or react with ash or basic groups in coal, thereby making the surface of coal lipophilic and improving affinity with heavy oil. It is believed that this improves the stability of the composition.

Further, in the present invention, the sedimentation property is improved by adding water to the composition, but its effect is not clear.

Effects of the Invention The pulverized coal oil mixed fuel composition obtained by the present invention maintains good stability over a long period of time, and the coal powder in the composition does not settle to the extent that it inhibits the fluidity of the composition. It has a low viscosity and is easy to handle. In particular, in the composition to which water is added in the second invention, coal sedimentation is particularly low, and even if the initial water content of the coal powder is somewhat high, it is possible to maintain a high degree of stability over a long period of time. can.

Furthermore, tall oil is obtained as a by-product during pulp production and is inexpensive, allowing the composition to be produced cheaply.

Mixed pulverized coal of example sample: The coal powder used in the test was Miike charcoal,
Tests using Minami-Oyubari coal, Warara coal, Taiheiyo coal, and Akahira coal were also conducted to examine the effects of coal production area.

In addition, the particle size of pulverized coal is 80% by weight of 200 mesh or less.
and 20% by weight of 120-200 meshes (A
), and in order to further examine the influence of grain size,
Tests were also conducted for 100% of 0 mesh or less (B) and 100% of 350 mesh or less (C).

The moisture content of the pulverized coal was adjusted to approximately 0.5% by drying it in a desiccator. A sample adjusted to .5% was also tested.

In addition, in order to understand the effect of adding water to the composition in the second invention of the present application, pulverized Miike charcoal containing about 1.5% water was used, and 0.3% of the total water content of the composition was used. weight%,
Compositions with added 0.8% and 1.8% water by weight were also tested.

Heavy Oil: As the petroleum heavy oil used in the composition, Arapianlite atmospheric distillation residual oil was used.

Additive: As an additive, tall oil fatty acid (Vertol FA-38 manufactured by Harima Kasei Kogyo Co., Ltd. (fat 188.1%)
, resin acid 7.4%, unsaponifiable matter 4.5%)), and the amount added was 1% by weight. 0.511%,
Additions of 3% and 5% by weight were also tested. For comparison, Neoperex NO, a commercially available surfactant containing sodium dodecylbenzenesulfonate as its main ingredient, manufactured by Kuhanadama Soap Co., Ltd., was used.

A sample containing 0.21% by weight of 1F powder) was also tested.

Blending ratio: pulverized coal was 50% by weight, tall oil fatty acid was used in a predetermined amount, and the remainder was heavy oil. However, for those to which water was added, the total of pulverized coal and water was 50% by weight. In addition, to examine the possibility of increasing the amount of pulverized coal, we increased the amount of tall oil fatty acids.
Pulverized coal 52.5% by weight, 55% by weight, 57.5% by weight
Also, a 60% by weight binding product was tested.

Preparation of Samples For formulations without the addition of water, samples were prepared by adding a predetermined amount of tall oil fatty acids and pulverized coal to heavy oil heated to 70°C, and then stirring for 3 minutes with a bladed stirrer. .

For formulations with added water, add a specified amount of tall oil fatty acids and water to heavy oil heated to 70°C, stir for 1 minute with a high-speed Chemitron to homogenize, and then homogenize the mixture into a specified liter of fine powder. Samples were prepared by adding charcoal and stirring for 3 minutes with a bladed stirrer.

Test Items Composition Stability Test Rod Penetration Test: A sample composition is placed at a depth of 2101 m into a glass cylinder with an inner diameter of 38 m1, and the sample composition is immersed in a constant temperature bath at 70°C and left.

After a predetermined period of time, a glass rod with a diameter of 5 nv and a weight of 20 g was dropped vertically from the liquid surface, and the percentage of the depth to which the glass rod penetrated into the sample was measured as the penetration rate. 1
In the case of 00% penetration, the time (seconds) required for penetration was measured and defined as the penetration time.

In this test, when the penetration rate is 100%, no hard sediment layer is formed at the bottom, and the flow is not actually inhibited. Also, the shorter the penetration time, the better.

Sedimentation Measurement of specific gravity of each layer: Place the composition in a glass cylinder similar to the above rod penetration test, turn it backwards at 70°C for a predetermined distance W, divide the composition into three parts, and divide the composition into three parts: the upper layer, the middle layer and the lower layer. About 101 tons were taken out from the center of each, and the specific gravity was measured using a pycnometer.

Viscosity: The viscosity of the sample composition at 70°C was measured using a coaxial rotating double cylinder viscometer (rheometer IR-200 manufactured by Iwamoto Seisakusho Co., Ltd.). To check the thixotropic properties of the composition, the rotational speed was changed to 50 r, p, i, (
The shearing rate was raised and lowered at a constant speed of 22/5 IJ) for 2 minutes, and the shear stress was continuously recorded. After that 50 r, p
The viscosity (Pascal/second) was measured by rotating for 5 minutes.

Table 1 shows the composition of the samples used in the sample test, and Table 2 shows the test results.

B: 100% below 200 mesh C: 100% below 350 mesh ■: Tall oil (1-1artallFA-33) N: Commercially available surfactant (NeoHlex No, IF powder) According to the above test results, additives In the case of blends without additives, even if the pulverized coal is Miike charcoal with small particle size and low water content, and is in the best condition, as shown in sample 1, after 7 days of sample preparation. The rod penetration rate had already not reached 100% on the day of the test, and the difference in specific gravity between the upper and lower layers of the sample had become large, indicating that the pulverized coal in the sample had settled significantly. Therefore,
Such a composition cannot be said to be of any use as a liquid fuel.

On the other hand, in standard sample 3 of the present invention, despite the large particle size, the rod penetration rate was 100% even after 15 days, and the penetration time was short. Furthermore, the difference in specific gravity between the upper and lower layers is small, and the viscosity is also low.

In sample 2 where the amount of tall oil fatty acid added was 0.5%, the rod penetration rate after 15 days did not reach 100%,
Although it cannot be said to be sufficient, it can be used for 7 days. In addition, in sample 4.5, in which the amount of tall oil fatty acid added was increased to 3 to 5%, the results were not significantly different from those of sample 3, and as long as the required amount of tall oil was added, even if the amount was increased further, there was no effect. No improvement can be expected.

In sample 6.7, in which the particle size of pulverized coal is small, although the viscosity is slightly higher, the rod penetration time is short and the difference in specific gravity between the upper and lower layers is also small. It can be understood that this improves the effect even more. It can be assumed that if 100% pulverized coal of 350 mesh or less is used, it is sufficient even if the amount of tall oil added is 0.5%.

Moisture contained in pulverized coal has an adverse effect on the effects of the present invention. In samples 8 and 9, which used pulverized coal with a high moisture content, the rod penetration rate was 100%, but
The penetration time is long, and the difference in specific gravity between the upper and lower layers is also large, indicating that the pulverized coal is settling rapidly. However, the viscosity of the composition was low, indicating that the bond between the particles of the settled pulverized coal was weak, and that it was easily stirred and dispersed by the rotation of the cylinder of the viscometer.

Therefore, it is considered that it can be used satisfactorily unless long-term stability is particularly required.

In the second invention of the present application, an example in which water is added to the composition is shown in Sample 10.11.12.

As is clear from the test results for this sample, even after 15 days had passed since sample preparation, the rod penetration time was extremely short, and the difference in specific gravity between the upper and lower layers was also extremely small. Therefore, although the basis for this is unclear,
It can be seen that by adding a small amount of water, a very stable composition can be obtained.

For those using pulverized coal other than Miike charcoal, sample 1
As shown in 3 to 16, even when 3% tall oil is added, the effect is inferior to that of Miike charcoal. When Minami-Oyubari charcoal is used, the same effect as Miike charcoal is obtained, but with Warara charcoal and Akahira charcoal, it is barely usable after 7 days, but after 15 days. In this case, the rod penetration rate did not reach 100%. There is also a large difference in specific gravity between the upper and lower layers. In Taiheiyo Coal, the rod penetration rate has not yet reached 100% after seven days.

However, even with these pulverized coals other than Miike charcoal, the stability is significantly increased compared to those formulated without adding tall oil, and by further increasing the amount of tall oil added or adding water, There is a possibility of obtaining a usable formulation. Moreover, if the storage period is short, the product can be used sufficiently.

Additionally, when using Miike charcoal and increasing its blending amount, the viscosity increases, as shown in samples 17 to 20.
Although the rod penetration time was longer, the rod purchase rate was 100%, and the difference in specific gravity between the upper and lower layers was small, so it can be said that the stability of the composition was sufficiently high. As long as the solid content concentration is high as a suspension of powder,
It is natural that the viscosity increases, and it is also natural that the rod penetration time increases accordingly. Despite this, the rod penetration rate is 100%, there is little sedimentation of pulverized coal in the composition, and the composition is sufficiently stable and can be used as a liquid fuel. However, in this case, it is necessary to increase the amount of tall oil added in accordance with the increase in the amount of pulverized coal.

However, even when the blended amount of pulverized coal is 60%,
Addition of 5% tall oil is sufficient; addition of 10% does not further improve stability as shown in sample 21.

For comparison, Sample 22 shows an example using a conventional surfactant as an additive, but the product of the present invention is comparable in some respects, and the viscosity is actually lower. It can be seen that the present invention has extremely excellent stability as a pulverized coal oil mixed fuel composition.

Claims (1)

[Claims] 1. 40 to 60 parts by weight of coal powder and 40 to 6 parts by weight of petroleum heavy oil
Pulverized coal oil mixed fuel composition 2, characterized in that 0.5 to 5 weight % of tall oil or tall oil fatty acid is added to 95 to 99.5 weight % of the mixture with 0 parts by weight. , Miike charcoal, 40 to 60 parts by weight of coal powder and 40 to 6 parts by weight of petroleum-based heavy oil.
0 parts by weight of tall oil or tall oil fatty acid and 0.5 to 5 parts by weight of water.
4. The pulverized coal oil mixture according to claim 3, wherein the coal is Miike charcoal. fuel composition